WO2006090643A1 - Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using same - Google Patents

Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using same

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Publication number
WO2006090643A1
WO2006090643A1 PCT/JP2006/302822 JP2006302822W WO2006090643A1 WO 2006090643 A1 WO2006090643 A1 WO 2006090643A1 JP 2006302822 W JP2006302822 W JP 2006302822W WO 2006090643 A1 WO2006090643 A1 WO 2006090643A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
fiber
carbon
yarn
spun
fibers
Prior art date
Application number
PCT/JP2006/302822
Other languages
French (fr)
Japanese (ja)
Inventor
Tatsuo Kobayashi
Naohiro Sonobe
Shigeki Iwamoto
Original Assignee
Kureha Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used
    • D03D15/12Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used using heat-resistant or fireproof threads
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16Yarns or threads made from mineral substances
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36Cored or coated yarns or threads
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0234Carbonaceous material
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00Inorganic fibres
    • D10B2101/10Inorganic fibres based on non-oxides other than metals
    • D10B2101/12Carbon; Pitch
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20Cellulose-derived artificial fibres
    • D10B2201/22Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24Viscose
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • D10B2505/02Reinforcing materials; Prepregs
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/56Manufacturing of fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2918Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2922Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2925Helical or coiled
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Abstract

Disclosed is a hybrid carbon fiber spun yarn comprising a core portion mainly containing carbon fibers and a sheath portion mainly containing carbon fibers and covering the outer surface of the core portion. Not less than 20% by mass of the fibers constituting the core portion are long-fiber-length carbon fibers having a fiber length of not less than 500 mm, and not less than 80% by mass of the fibers constituting the sheath portion are short-fiber-length carbon fibers having a fiber length of less than 500 mm. The mass ratio between the long-fiber-length carbon fibers and the short-fiber-length carbon fibers (long-fiber-length carbon fibers : short-fiber-length carbon fibers) is from 20:80 to 80:20.

Description

Specification

Bruno, yarn Iburitsudo carbon fiber spinning and hybrid carbon fiber spun yarn fabric using the same

Technical field

[0001] The present invention, concerning the solid polymer electrolyte fuel gas diffuser for a battery (collector) c Iburitsudo carbon fiber spun yarn useful for such and it Yore was the hybrid carbon fiber spun yarn fabric .

BACKGROUND

[0002] Currently, as the carbon fiber, so-called PAN-based carbon fibers polyacrylonitrile (PAN) as a raw material, so-called rayon-based carbon fibers and rayon as raw materials, as well as so-called pitch-based carbon fibers and pitch such raw materials are manufactured, it is further manufactured anisotropic carbon fibers and isotropic carbon fibers as the pitch-based carbon fibers. Among these, pitch-based isotropic carbon fibers, the raw material is relatively inexpensive and inexpensive, and because the production method is perforated advantage for mass production, light weight, chemical resistance, heat resistance, sliding resistance and a conductive It is widely used in applications where properties such as sex are required.

[0003] In addition, carbon fibers, filaments, slivers (fiber bundle), spun yarn, woven fabric, chopped, mill de, mats are used in many forms such as Puripureda, varying also the firing temperature, carbon degree by application Erareru . Among them, carbon fiber spun yarn and the carbon fiber fabric, insulation, sliding material, which is utilized as a construction material such as a conductive material, in particular of the gas diffuser or the like for a solid polymer electrolyte fuel cell to electronic materials utilization is achieved of.

[0004] Therefore, In such a carbon fiber spun yarn and the carbon fiber fabric, flexibility and conductivity in addition to the gas-permeable, even adhesion between the matrix material such as a polymeric material, a uniform fineness and thickness sex, has come to a high tensile strength, etc. are required.

[0005] Here, with respect to the conductive carbon fiber spun yarn and the carbon fiber fabric, they were heat-treated at a high temperature of over 900 ° C or more, it is possible to obtain a high conductivity by increasing the carbonization degree.

[0006] Further, if using a carbon fiber woven fabric as a solid polymer electrolyte fuel cell gas diffuser, its gas permeability is determined by the aperture ratio (porosity), gas diffusers in very coarse porous material contact with the catalyst layer becomes defective causing problems to the current collector when used as. Further, the filaments woven single yarn are aligned is the aperture ratio (porosity) problem of low reduced gas permeability. Therefore, as such carbon fiber fabric, Yasure become dense equipped with single yarn, it is preferable of the spun yarn woven fabric than the filament fabric. In consideration of diffusion of the reaction gas to the catalyst layer, it is necessary to appropriately control the thickness of the carbon fiber woven fabric to be used as a gas diffuser.

[0007] Therefore, the carbon fiber woven fabric used as a gas diffuser, the method of the spun yarn woven fabric to obtain a preferred instrument such spun yarn fabric and having a 900 ° C or more thermal history has a suitable thickness to a method of a method of heat-treating the fabric obtained by weaving the spun yarn oxidized fiber or carbon-fiber at 900 ° C or higher temperatures, by weaving the spun yarn that has been heat treated at 900 ° C or higher and fabric There adopted is, Ru.

[0008] Examples of such carbon fiber spun yarn, spun yarn of oxidized fiber force PAN-based spun yarn of spun yarn and pitch-based PAN-based flame-resistant fiber is known when the heat treatment at 900 ° C extreme strength decreases, it is difficult to weaving. Therefore, if adopting a method of heat treatment at 900 ° C after weaving the oxidized fiber, such can be obtained fabric of interest Le. While with force, in that case, since it causes a reduction in the strength of the spun yarn by the strain and heat treatment of the fibers by heat treatment, the strength of the resulting fabric has a drawback that low. Also, the use of long fiber length carbon fibers as carbon fiber PAN-based continuous filaments, there is a problem that adhesion between the obtained that the spun yarn and the matrix material will be poor.

[0009] Therefore, for example, JP 2002- in 352807 discloses, the porous carbon substrate fiber length is collectively in a state in which carbon fiber 25~80mm had voids, particulate fluororesin force ^ ~ 40 wt % included, and the gas diffuser, wherein the granular fluororesin is coupled between said carbon fibers as a binder is disclosed. Furthermore, JP 2003 one 288 906 No. Ore in Japanese Te, on at least one surface of the electrode the carbon fiber fabric, the gas diffuser, characterized by having a carbon layer containing Kaponpu rack and fluororesin is disclosed. And force, while the binder and carbon particle-like fluororesin for tensile strength of the carbon fiber spun yarn itself has been described to improve the tensile strength of the carbon fiber woven fabric obtained low ingredients in Patent Documents 1 and 2 current collecting function inevitably gas diffuser is disadvantageously lowered from using layers.

[0010] Further, in JP 53- 81735 discloses, 25 mm or more, preferably carbon-containing fiber yarn having improved strength by spinning a sliver-like carbon fiber having a fiber length of 50~75mm it has been proposed to obtain. While force and in this way its tensile strength even-carbon fiber spun yarn obtained is about 0. 08~0. 09N / tex, were not yet a ten minutes.

[0011] On the other hand, pitch-based isotropic carbon fibers, staple fibers length is most are commercially available spun yarn with improved carbonization it as a raw material. And power, while, the carbon textiles spun yarn which is commercially available, has sufficient tensile strength and fineness variation is small les, what was not. Therefore, it was not yet sufficient in terms of it obtained by weaving fabric strength and thickness variations.

Disclosure of the Invention

[0012] The present invention, the has been made in view of the problems of the prior art, to achieve a high tensile strength without lowering the adhesion with the matrix material, such as polymeric materials, moreover fineness uniform excellent carbon fiber spun yarn to sex, and excellent adhesion and mechanical strength of the matrix material, yet is an object that you provide a carbon fiber spun yarn fabric excellent in uniformity in thickness.

[0013] The present inventors have found, after intensive studies to solve the above problems, a core section composed mainly of fiber length 500 meters m or more long fiber length carbon fibers, short fibers of less than a fiber length 500mm by covering the outer peripheral portion mainly composed of long carbon fibers, hybrid carbon fiber spun yarn of the object can be and achieve child is heading can be obtained, and have completed the present invention.

[0014] Hybrid carbon fiber spun yarn of the present invention, the hybrid carbon fiber spun yarn comprising a core section composed mainly of carbon fibers, and an outer circumferential portion covering an outer circumferential surface of and the core portion composed mainly of carbon textiles a is, more than 20% by weight of the fibers constituting the core portion is longer than the fiber length of carbon fibers having a fiber length of 500mm, short fibers more than 80% by weight of the fibers constituting the outer peripheral portion is less than the fiber length 500mm a long carbon fiber, and the weight ratio of the said long fibers long carbon fiber short fiber length of carbon fibers (long fiber length carbon fibers: short fiber length of carbon fibers) 20: 80-8 0: those 20 it is.

[0015] The hybrid carbon fiber spun yarn fabric of the present invention, the hybrid-carbon fiber spun yarn of the present invention are those containing more than 30 wt%.

[0016] In the above hybrid carbon fiber spun yarn of the present invention, the long fiber length of carbon fibers

, Is preferably at least one carbon fiber selected from the pitch-based anisotropic carbon fibers, polyacrylonitrile-based carbon fibers and rayon-based carbon fibers force the group consisting of.

[0017] Further, in the above hybrid carbon fiber spun yarn of the present invention, the short fiber length of carbon fiber is preferably a pitch-based isotropic carbon fibers and Z or polyacrylonitrile-based carbon fibers.

[0018] Furthermore, said in the hybrid carbon fiber spun yarn of the present invention, the long fiber length of carbon fibers are polyacrylonitrile-based carbon fibers, and the short fiber length of carbon fibers are pitch-based isotropic carbon fibers It is preferred.

[0019] Further, in the above hybrid carbon fiber spun yarn of the present invention, the proportion of carbon fiber and less than 500mm in fiber length 150mm or more in the short fiber length of carbon fibers 3-3

Les, Shi preferred that 0% by mass.

[0020] Further, in the above hybrid carbon fiber spun yarn of the present invention, the outer peripheral portion is configured of a twisted yarn composed mainly of said short fiber length of carbon fiber, the yarn is the length fiber 維長 carbon fibers Les outer peripheral surface of the core portion by being twisted together with the core section composed mainly is covered with the twisted yarn, Le Shi preferred is Rukoto.

[0021] In the hybrid carbon fiber spun yarn of the present invention,

(I) that the number of twist in the hybrid carbon fiber spun yarn is 50 to 400 times / m,

(ii) the density of the long fiber length of carbon fibers are 1. 7 to 2 3 g / cm 3, and the density of the short fiber length of carbon fiber 1. 5:. 1. It is 8GZcm 3,

(Iii) mass per lOOOm (tex) that is force ¾0~150G,

It is preferred.

[0022] In addition, a high tensile strength without lowering the adhesion with the matrix material of a polymer material such as In the hybrid carbon fiber spun yarn of the present invention are achieved, moreover also excellent uniformity of fineness become reason necessarily clear at the a record, but the inventors are estimated observation as follows.

[0023] That is, first, in the hybrid carbon fiber spun yarn of the present invention, because it is composed of long fiber length carbon fibers having a tensile strength that the core portion is not higher as a main component, a high tensile strength is achieved that. In more detail, the spun yarn is a long fiber bundle obtained by connecting the short fibers by entangling short single fibers by applying a twist to the short fibers. Its tensile strength Therefore, is maintained by the frictional force generated by the single fibers entangled (contact), the contact area between fibers The more entanglement increases, friction increasing, intensity increases and thus. Furthermore, the stronger twist, will be fibers are strongly pressed et al, frictional force is increased, the tensile strength is to be enhanced as a spun yarn. Also, since the joining point of the fibers longer fiber length to be used is reduced, so that the strength of the spun yarn that is obtained is improved. Te hybrid carbon fiber spun yarn odor of the present invention, the core is configured as a main component fiber length 500mm or more long fiber length carbon fiber, a short fiber length of carbon fiber below its outer periphery fiber length 500mm since that is the coated configurations, the present inventors have high tensile strength as described above can be achieved is presumed.

[0024] In the hybrid carbon fiber spun yarn of the present invention, although the core is constituted by a long fiber length carbon fibers having poor adhesion to the matrix materials, often its outer peripheral surface of the surface fluff short because it is covered by the fiber length of carbon fibers, which adhesion to the matrix material is kept sufficiently at a high not state the surface fluff anchor effect of the carbon fibers that make up the outer peripheral portion and the present inventors inferred to.

[0025] Further, in the hybrid carbon fiber spun yarn of the present invention, variation in fineness is constituted its core by less 且 one strong tensile strength long fiber length carbon fibers, constituting the outer peripheral portion thereof core short fiber length because it is configured with twisted together with the carbon fibers, than the tensile strength is strong spun yarn formed by using only the short fiber length of carbon fibers. Further, it is possible to shorten the fiber length of the carbon fibers constituting the outer peripheral portion, therefore, as a hybrid yarn, so-called slabs, but also generating a massive part which are said to fly is sufficiently prevented and the present inventors inferred to.

[0026] Then, the hybrid carbon fiber spun yarn fabric of the present invention is thus with hybrid-carbon fiber spun yarn adhesion excellent and tensile strength was excellent in uniformity of Kogu Moreover fineness of the matrix material since the resulting Te, excellent adhesion and mechanical strength of the matrix material, the tooth force also becomes excellent in uniformity in thickness. Further, Ore hybrid carbon Textile spun yarn fabric of the present invention, Te is reasonable aperture ratio of the fabric which is Nag hybrid carbon fiber spun yarn to each other closely to each other for surface fuzz outer peripheral portion constituting it for (porosity) is retained, the present inventors when becomes excellent in gas permeability is inferred.

According to [0027] the present invention, to achieve a high tensile strength without lowering the adhesion with the matrix material, such as polymeric materials, tooth force, the carbon fiber spun yarn excellent in uniformity of fineness also and excellent adhesion and mechanical strength of the Matrix material, tooth force, it becomes possible to provide an excellent-carbon fiber spun yarn fabric in the thickness uniformity.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] [FIG. 1] FIG. 1 is a block diagram showing a preferred carding machine for use in the carding step in the process of obtaining the short fiber length of carbon fiber bundles mowing force to the invention.

FIG. 2 is a block diagram showing a preferred kneading Article machine for use in Nerijo step of the process of obtaining the short fiber length of carbon fiber bundle according to the present invention.

FIG. 3 is a block diagram showing a preferred spinning machine for manufacturing the hybrid carbon fiber spun yarn of the present invention.

[4] FIG. 4 is a block diagram showing a preferred twisting machine to produce a brittle strands of a hybrid carbon fiber spun yarn of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0029] Hereinafter, will be described in detail with reference to the hybrid carbon fiber spinning 績糸 fabrics their preferred embodiment of a hybrid carbon fiber spun yarn and the invention of the present invention.

[0030] First, a description will be given hybrid carbon fiber spun yarn of the present invention.

[0031] Hybrid carbon fiber spun yarn of the present invention, the hybrid carbon fiber spun yarn comprising a core section composed mainly of carbon fibers, and an outer circumferential portion covering an outer circumferential surface of and the core portion composed mainly of carbon textiles a is, more than 20% by weight of the fibers constituting the core portion is longer than the fiber length of carbon fibers having a fiber length of 500mm, short fibers more than 80% by weight of the fibers constituting the outer peripheral portion is less than the fiber length 500mm a long carbon fiber, and the weight ratio of the said long fibers long carbon fiber short fiber length of carbon fibers (long fiber length carbon fibers: short fiber length of carbon fibers) 20: 80-8 0: those 20 it is.

[0032] fiber constituting the core part of the hybrid carbon fiber spun yarn of the present invention, the 20 wt% or more (preferably 50 wt% or more, particularly preferably 80 mass% or more) of fiber length 500mm than the (preferably the above 1000 mm, particularly preferably long fiber length carbon fibers 3m or more). Content is 20 wt% non Mitsurude of the long fiber length of carbon fibers in the fiber constituting the core part, the tensile strength of the hybrid carbon fiber spun yarn obtained is lowered.

[0033] As long fiber length carbon fiber according to the present invention, pitch-based anisotropic carbon fibers, Poriatari Ronitoriru based carbon fibers (PAN-based carbon fiber), and a rayon-based carbon fibers. Among these, the use of polyacrylonitrile-based carbon fibers (PAN-based carbon fibers), the cost is relatively cheap, further improve the uniformity of the tensile strength and the fineness of the hybrid carbon fiber spun yarn, from the viewpoint of improving the uniformity of the tensile strength and the thickness of the hybrid carbon fiber spun yarn fabric. The average diameter of the long fiber length of carbon fibers according to the present invention is particularly limited, such les, but 5: is preferably used of about 15 μ ΐη. The average diameter of the long fiber 維長 carbon fiber Hosore, it is preferred Shi Le, but not preferred because manufacturing productivity is degraded less than the above lower limit. On the other hand, or more than the upper limit the tensile strength decreases, ease cause yarn breakage when twisting les, since Preferably Do Re.

[0034] core of the hybrid carbon fiber spun yarn of the present invention is the long fiber length of carbon fibers in which account for more than 20 mass%, as a component other than the long fiber length of carbon fiber, less fiber length 500mm and short fiber length of carbon fibers, polyamide fibers, polyester fibers, acrylic textiles, may contain synthetic resin fibers such as polyethylene terephthalate fibers.

[0035] The long fiber length carbon fiber constituting the core part of the hybrid carbon fiber spun yarn of the present invention, Yo be made with twine les, but may be a fiber bundle that is not twisted.

[0036] Further, the force in the present invention, mow long fiber length carbon fiber has a density of from 1.7 to 2. Intended preferably 3g / cm 3 1. 7~2. 0g / cm 3, particularly preferably 1 . 7: are those of 1. 9g / cm 3. Less than density of 1. 7 g / cm 3 of the long fiber length of carbon fibers tend to intensity of insufficient carbon fiber carbide is reduced, while the strength of the carbon fiber exceeds the upper limit and crystallization proceeds excessively there tend to be reduced.

[0037] Further, the manufacturing method of the long fiber length of carbon fibers according to the present invention is not particularly limited, for example, a method of carbonizing the acrylic fibers (PAN fibers), rayon fibers, Mesofuwe one Zupitchi carbon fiber Yo Le, be used, and the like method, a commercially available record, Ru long fiber length carbon fiber such Sufuaito base manufactured by Toho Tenax Co., Ltd. to.

[0038] In addition, the long fiber length of carbon fibers according to the present invention, from the viewpoint of further improving the tensile strength, it is adjusted to preferably implement its carbon degree that is carbonized before Bosekika卩E it is more preferable that the additional heat treatment is applied for. Such a heat treatment temperature for the carbonization generally had sigma preferred about 800 to 3000 ° C, approximately from 900 to 2000 ° C in general as the heat treatment temperature for adjusting the carbon degree It is preferred.

[0039] fiber constituting the outer peripheral portion of the hybrid carbon fiber spun yarn of the present invention, the fiber length is the proportion of the carbon fibers of less than 500mm is 80 mass% or more, the following proportions of the carbon fiber 300mm is 80 wt% it is further desirable ratio of the preferred tool 200mm or less of the carbon fiber to be more than 80 mass% or more. Wherein the fibers constituting the outer peripheral portion in the short fiber length less than the content of 80 mass% of the carbon fibers, the adhesion between the matrix material of the hybrid carbon fiber spun yarn obtained is lowered.

[0040] In the short fiber length of carbon fiber mowing force to the invention, the fiber length is preferably fixture 5-20 quality that a ratio 3 to 30 wt% of the carbon fibers of less than 且 one 500mm in 150mm or more and more preferably in an amount%. The ratio of the carbon fibers is less than the above lower limit, there is a tendency that tensile strength of the hybrid carbon fiber spun yarn obtained is lowered. On the other hand, when the ratio of the carbon textiles exceeds the upper limit, by passing between the stretching (rpm different roller several times the number present in the fiber bundle in kneading Article machine when producing spun yarn from the fiber bundle drawing the fiber bundle) is made in step to further improve the parallelism of the fibers as one fiber bundle is likely to occur connexion yarn breakage of longer fiber length than between rollers septum and be variation in fineness slab tends to lump unit called a fly is likely to occur.

[0041] On the other hand, the carbon fiber having a fiber length of less than 150mm, the carding machine and a force generally predominantly less than 50 m m 150mm in which the carbon fibers in the raw material is formed is cut appropriately in process step by kneading Article machine of those having a fiber length, it is preferred that this contains from 97 to 70 wt% at moderate distribution in the short fiber length of carbon fiber mowing force to the invention. If the fiber length is spinning process only more carbon fiber 150mm is cause thickness unevenness of the hybrid carbon fiber spun yarn obtained, the result thickness unevenness of the fabric is in the easily tends to occur as.

[0042] Further, as the short fiber length of carbon fiber mowing force to the invention, pitch-based isotropic carbon fibers, polyacrylonitrile-based carbon fibers (PAN-based carbon fibers) force and the like S. Be used pitch-based isotropic carbon fiber Among these, the more improved the adhesion between the matrix material les, preferably from cormorants viewpoint. Furthermore, the average diameter of the short fiber length of carbon fibers according to the present invention is not limited especially, it is preferable to use of about 5 to 20 xm. The average diameter of the short fiber length carbon textiles is Ri Do difficult connexion handle a weak tensile strength of the fiber is less than the above lower limit, dust is in many tend, on the other hand, sharply the number of carbon fibers exceeds the upper limit there is a tendency to decrease.

[0043] outer periphery of the hybrid carbon fiber spun yarn of the present invention, wherein at short fiber length of carbon fibers in which accounts for at least 80 mass%, the as components other than the short fiber length of carbon fibers, fiber length 500mm or more and the long fiber length of carbon fibers, polyamide fibers, polyester fibers, Atarinore fibers may include synthetic resin fibers such as polyethylene terephthalate fibers.

[0044] The short fiber length of carbon fiber constituting the outer peripheral portion of the hybrid carbon fiber spun yarn of the present invention, it is preferable instrument 20 mass% or more which is a twisted yarn, preferably 40 wt% or more, in a further preferred more preferred arbitrariness is that the outer peripheral portion is constituted by 80 wt% or more of the twisted yarn.

[0045] In addition, the short fiber length of carbon fibers according to the present invention has a density of 1. 5: 1. Preferably intended 8g / cm 3 1 · 5~: ! · 7g / cm 3, particularly preferably 1 - 55: are those of 1. 7g / cm 3. Density of the short fiber length of carbon fibers is less than the lower limit tends you decrease insufficient tensile strength carbonization, while there is a tendency that wettability is deteriorated and the resin exceeds the above upper limit.

[0046] Further, the manufacturing method of the short fiber length of carbon fibers according to the present invention is not particularly limited, for example, the aforementioned can be used to cut short the long fiber length of carbon fiber, moderate length of be used as it is in the case of short fiber length of carbon fibers having, it may be used after controlling the fiber 維長 by an appropriate cutting machine.

[0047] As a spinning method for pitch-based short fiber length of carbon fibers, centrifugation issuing Nozunore whether we molten pitch by utilizing the centrifugal force, the molten pitch blown with hot high velocity air Merutopuro one method, melt-blown the hot high velocity air and vortex 卷状, vortex method of stretching in the swirling flow, drawn by suction the fibers air sucker nozzle, there is Easa Tsu mosquito one way such that condenses cotton at its outlet after, any of these it can be used short fiber length of carbon fiber bundle and a carbon fiber mat obtained by the method.

[0048] As a method for producing short fiber length of carbon fibers according to the present invention, for example following are just a few methods are preferably employed. That is, first, after cutting appropriately by a-carbon fiber used as a short fiber length of carbon fiber cutting machine, to obtain a carbon fiber bundle aligned pull the fibers by construction of Kezumen machine as shown in FIG. In such Figure 1 shows carding surface machine, first, inserted from the carbon fiber Ma Tsu sheet 1 is back roller 2, after being sprayed with oil 3, the fiber is aligned off at Fuora 4, relative to the back roller 2 the fibers are drawn by the peripheral speed ratio between the front roller 5 and the back port over La 2 rotating at a larger peripheral speed. Then, through the apron 6, sliver-like carbon fiber bundle 7 are taken plated on coiler 8.

[0049] Next, the configuration of the kneading Article machine as shown in FIG. 2, a combination of carbon fiber bundle of several (doubling), as one carbon fiber bundle while stretching (draft) a length of several times together to further improve the parallelism of the fibers, the fibers are further narrowed. The kneading Article machine shown in this FIG 2, first, a carbon fiber bundle of a plurality of drawn from product casing 11 is I if in creel stand 12, through the acrylic guides 13 and sliver guide 14, a back roller 15 It is derived. Then, further the carbon fiber bundle is passed through feed the middle roller 16, the fibers with pulling assortment Erareru in Fuora 17, the front roller 18, passed through feed between the nip roller 19 and the top roller 20. Carbon fiber bundle was stretched in the meantime undergoes a sliver guide 21, it will be stored on any product casing 23 and through the roller 22. In addition, it may also be to go through several times such Nerijo process Les,.

[0050] In addition, the short fiber length of carbon fibers according to the present invention, from the viewpoint of further improving the tensile strength, it is preferable that the heat treatment in a state before the spun yarn are subjected. Examples of such a heat treatment temperature, force S preferably about 700-3,000 ° C, more preferred arbitrariness about 800 to 1500 ° C.

[0051] Hybrid carbon fiber spun yarn of the present invention includes a core portion shall be the main component long fiber length carbon fibers described above, and an outer peripheral portion mainly composed of short fiber length of carbon fiber described above, It said outer peripheral portion covers the outer peripheral surface of the core.

[0052] In the hybrid carbon fiber spun yarn of the present invention, the long fiber length carbon textiles and the short fiber length weight ratio of the carbon fiber (the long fiber length of carbon fibers: short fiber length of carbon fibers) 20 : 80 to 80: it mosquito preferably 20, 30: 70-70: 30 Dearu Kotokayori preferred Rere. The content of the pre-Sulfur butterfly fiber length of carbon fiber is less than the lower limit, tensile strength of the hybrid carbon textiles spun yarn obtained is lowered, while the the short fiber length less than the content ratio is the lower limit of the carbon fibers, resulting adhesion between the hybrid carbon fiber spun yarn and the matrix material is low down to be.

[0053] In the hybrid carbon fiber spun yarn of the present invention, the if the outer circumferential surface of the core portion is long covered by the outer peripheral portion Yogu its specific configuration is not particularly limited, the outer peripheral portion is the short the fiber length of carbon fiber is composed of a twisted yarn made mainly, the outer peripheral surface of the core portion by being twisted together with the core portion thereof twisted yarn is mainly composed of long fiber length carbon fibers is covered by said twisted yarn Les, is Rukoto Le, Shi preferred Te.

[0054] Further, the thickness of the hybrid carbon fiber spun yarn of the present invention is not particularly limited, in units of tex showing a mass (g) per 1000 m, it forces S preferably about 30~500tex, 3 0~ : it is more preferable tool 30 is about 150tex:! it is particularly preferred to be about OOtex is even more good Mashigu 30~80tex about. Located hybrid carbon fiber spinning thickness is not thinner fabric obtained exceeds the upper limit trends 績糸 of the present invention, on the other hand, is less than the lower limit, not suitable strength can not be obtained for weaving, further obtain It is gas permeability of the fabric tends to decrease.

[0055] Further, in the hybrid carbon fiber spun yarn of the present invention, to exert the effect on the number of twist strength, force, mow twist number, it is preferable instrument 100 to 200 times is 50 to 400 times Zm more preferably / m. When this number of twists exceeds the upper limit fibers tend to come out could be destroyed, the other tends to tensile strength of the hybrid carbon textiles spun yarn obtained is less than the lower limit is lowered. Incidentally, the hybrid carbon fiber spun yarn of the present invention may be used in doubling the twister in combination two or more. In such a case, for example, in the case of the two, as a secondary twist to the primary twist is preferably exerted is twist reverse rotation of twist of 60% ± 5%. In the case of three, as a secondary twist to the primary twist is preferably exerted it is twist reverse rotation of twist of 55% ± 5%.

[0056] Hybrid carbon fiber spun yarn of the present invention, as a result has a configuration as described above, it is possible to have a high level of tensile strength of 0. 35N / tex or more, more preferably 0. 40NZtex it is possible to have a very high level of tensile strength of more than.

[0057] The method of manufacturing a hybrid carbon fiber spun yarn of the present invention as described above is not particularly limited, the following method is preferably adopted if example embodiment. That is, in the configuration of the spinning machine as shown in FIG. 3, the when twisted further stretched 'pressurized carbon fiber bundles of short fiber length of carbon fiber, the long fiber 維長 carbon fibers of the long fiber for use as a carbon fiber to blend was put a bunch from the middle roller. In the spinning machine shown in this FIG. 3, first, the short fiber length of carbon fiber bundle 32 from product casing 31 through the creel stand roller 33, guided to the back roller 34, while the length the fiber length of carbon fiber bobbin 35 carbon fiber bundle 36 is introduced from the middle rollers 37. Then, Ebb Ron 38, between which is passed sent between the bottom 39 and the front roller 40, together with short fiber length of carbon fiber bundle 32 is stretched by the peripheral speed ratio between the front roller 40 and back roller 34, a long fiber It is combined with long carbon fiber bundle. Subsequently, through both fiber bundles force S Snell guide 41 together, is twisted by a spindle 44 comprising a ring 42 and a brake pedal 43, taken plated on wind-up bobbin down 45. In this way, it is possible to obtain a hybrid carbon fiber spun yarn of the present invention.

[0058] Incidentally, the hybrid carbon fiber spun yarn of the present invention, it is a single twisted yarn, but is advantageous in Ru give thin thread, if necessary, a twisting machine having a configuration as shown in FIG. 4 can also be also be a thread that Ri twisted filtered using. The twisting machine shown in this FIG. 4, first, two single strands are combined in Tari Le stand 51, through a sliver guide 52, the front guide 53 and Snell guide 54, the spindle 57 comprises a ring 55 and a brake pedal 56 by being twisted, taken plated on wind-up bobbin 58. In this way, it is possible to obtain the hybrid carbon fiber spun yarn of even filter strands.

[0059] Next, a description will be given hybrid carbon fiber spun yarn fabric of the present invention.

[0060] Hybrid carbon fiber spun yarn fabric of the present invention, the hybrid carbon fiber spun yarn of 30% by mass or more (more preferably 40 mass% or more) of the present invention are those which contain. The containing organic proportion of the hybrid carbon fiber spun yarn in the hybrid carbon fiber spun yarn fabric is less than 30% by weight of the present invention, reduces the adhesion between the resulting fabric a matrix material, further resulting fabric mechanical strength improvement is not achieved.

[0061] Specific weave to obtain a hybrid carbon fiber spun yarn fabric of the present invention is not particularly limited, for example, plain weave, Ri satin, twill, are employed such basket weave is appropriate, among them a plain weave Ri is preferred.

[0062] Further, when obtaining the hybrid carbon fiber spun yarn fabric of the present invention, the hybrid carbon fiber spun yarn of the present invention, the intensity may be used as at least one of effectively capitalize warp or weft but warp Les, more preferably be used a hybrid carbon fiber spinning 績糸 of the invention and both weft.

[0063] Incidentally, the hybrid carbon fiber spun yarn fabric of the present invention, wherein at hybrid-carbon fiber spun yarn of the present invention is one that accounts for at least 30 mass%, as components other than the Haipuriddo carbon fiber spinning 績糸, other or carbon fiber spun yarn, polyamide fibers, polyester fibers, may be included spun yarn made of acrylic fibers, synthetic resin fibers such as polyethylene terephthalate fibers.

[0064] This way, the hybrid carbon fiber spun yarn fabric of application of the present invention thus obtained is not particularly restricted, it is particularly suitable as a gas diffuser for a solid polymer electrolyte fuel cell

[0065] The volume resistivity of the hybrid carbon fiber spun yarn fabric of the present invention as described above, preferably 2 0~: 1500 μ Ω · πι, more preferably ί or 50 to 700 mu Omega 'm, particularly preferably ί or 50 it is ~400 μ Ω • m. The hybrid carbon fiber spun yarn fabric FAW (Fiber Area Weight) ί 50~600g / m 2 force S Preferably the present invention, preferably from 70~400g / m 2 force S, 80 to 200 g / m 2 is particularly preferred. When used as a gas diffuser, the fabric of FAW exceeds the upper limit, although the current collecting ability is improved, Ri tended voids is less and less gas permeability decreases, while the fabric of FRW is the lower limit by weight, reduces the contact with the catalyst layer, collector capacity tends to decrease.

[0066] In addition, the thickness of the hybrid carbon fiber spun yarn fabric of the present invention is not particularly limited, 0. 10~1. OOmm force S Preferably, preferably from 0. 10.about.0. 60 mm force S, 0.. 10 to 0. 40m m is particularly preferred. When used as a gas diffuser, if the thickness of the fabric exceeds the upper limit, there is a tendency that air permeability is less likely to be maintained, while it is less than the lower limit, decrease the time power consuming battery performance on the diffusion of the reaction gas They tend to be.

Example

[0067] Hereinafter, a more detailed explanation of the present invention through examples and comparative examples, the present invention is not limited to these. Incidentally, adhesion of the density of the carbon fiber, the tensile strength of the spun yarn, the spun yarn and the matrix material, and the thickness of the spun yarn woven fabric were respectively evaluated or measured by the following method.

[0068] (i) Density measured by density gradient tube method

(Preparation of specific gravity liquid)

After weighed prescribed amount of zinc chloride and 1% hydrochloric acid in a beaker and mixed. The resulting mixture was transferred to a graduated cylinder of 500 ml, was measured 20 ± 1. 0 ° gravity smiling hydrometer after a temperature of 20 soil 1. 0 ° C by immersion in cold thermostat bath of C. It was prepared 10 kinds of specific gravity solution by changing the relative amounts of zinc chloride and 1% hydrochloric acid as appropriate.

[0069] (Density Measurement of the sample)

In 20ml graduated cylinder, by each 2ml said 10 kinds of specific gravity liquid, high forces of gravity, et gently poured while transmitted the tube wall, made a density gradient tube. On the other hand, the carbon fiber sample of about 0. lg of standard sieves were passed in sliding crush mesh 0.99 mu m in a mortar to obtain a sample dispersion liquid was dispersed in a small amount of ethanol. Then immersed the density gradient tube to a low temperature thermostat bath of 20 ± 1. 0 ° C, after 30 minutes, gently placed sample dispersion in a density gradient tube was allowed to stand for 12 hours or more. Or more after 12 hours, it reads the position of the sample in the density gradient tube to determine the density of the sample using a density conversion table.

[0070] (ii) bow I Zhang strength measurements of the spun yarn

Tensile tester (KK Orientech, Ltd., "Tensilon universal tester 1310 Model") with the chuck distance of the spun yarn and 300 mm, tensile its spun yarn rupture strength when pulled at a speed 200 mm / min divided by the tex, and the tensile strength of the spun yarn.

[0071] (iii) Evaluation of Adhesion of the matrix material

It was determined adhesion between the spun yarn and the matrix material by the following method. That is, phenol resin (Gunei Chemical Industry Co., Ltd., "PL-4804") a hybrid carbon textiles spun yarn fabric impregnated with dried by forced air at 24 hours 40 to 80 ° C (hybrid carbon fiber spun yarn fabric 38 to 46 wt%, after repeated) the impregnated and dried as Madeko which the mass ratio in the range of phenolic resin 54 to 62 wt%, laminated ten, temperature 170 ° C, pressure 0 · 06MP after 1 hour press forming 'curing at a, and heat treated for one hour in a vacuum oven 2000 ° C. Then removed furnace power, as a sample, and disconnect with a cutter so as the cut surface passes through the substantially central portion of the sample was visually observed and the cut layer surfaces at room temperature. Then, it passed if no crack between laminated hybrid carbon fiber spun yarn fabric (A), was determined otherwise Fugo rating and (C). (Iv) the thickness measurement of the spun yarn woven fabric

The carbon fiber cloth test method to measure the thickness of the spinning 績糸 fabric in accordance with the method 1 described in JCFS 003- 1982. That is, test pieces five lOOmm X IOOmm, straight type paper micrometer "PPM_ 25 Model" (Mitutoyo Corporation Ltd.) was used, in parallel to the measuring plane sample surface by gently rotating the spindle contact, read the scale when the ratchet were standing three Kaion. The average value of the measured values ​​was calculated to two decimal places.

[0072] (Production Example 1) Heat treatment temperature 1000 ° C, the production of pitch-based isotropic carbon fiber bundle of 660tex

Pitch-based isotropic carbon fiber bundles (Co. Kureha, sagging force toe T-101S, 23 g / m) using, in Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2 , it extends in the 0-fold 4. Place this carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 5. It was stretched to 3 times a one carbon fiber bundle, and further stretched in the third 3 times 5. Place this carbon fiber bundle 2 with kneading Article machine and one carbon fiber bundle, further fourth the carbon fiber bundle in kneading Article machine two combined 5. stretched 0 times to obtain a pitch-based isotropic carbon fiber bundle of one 0. 6 6g / m (660te X ).

[0073] Ltd. (Production Example 2) heat treatment temperature 1000 ° C, a pitch-based isotropic carbon fiber bundle of 920tex 诰

Pitch-based isotropic carbon fiber bundles (Co. Kureha, sagging force toe T_ 101S, 23 g / m) using, in Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2, extend in the 0-fold 5. Place this carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machines 5.0 extend in the multiplying and one carbon fiber bundle, further to extend the one carbon fiber bundle of the 0-fold 4. the carbon fiber bundle 2 together with the third kneading Article machine, further a fourth kneading Article machine 4. the carbon fiber bundle 2 together with stretched 0 times to obtain a pitch-based isotropic carbon fiber bundle of one 0. 9 2g / m (920te X ).

[0074] (Production Example 3) heat treatment temperature 1000 ° C, the production of pitch-based isotropic carbon fiber bundle of 398tex

Pitch-based isotropic carbon fiber bundle used (Co. Kureha, sagging force tow T- 101 S, 23g / m), and Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2 in, the one carbon fiber bundle in the first kneading Article machine 5. stretched 0 times and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 5. extend in the 0-fold and one carbon fiber bundle, and one carbon fiber bundle and further stretched 3 times 4. the carbon fiber bundle 2 together with the third kneading Article machines, the additional fourth the carbon fiber bundle in kneading Article machine two combined 4. stretched three times to obtain a pitch-based isotropic carbon fiber bundle of one 0. 398g / m (398tex).

[0075] (Production Example 4) Heat treatment Temperature 1000 ° C, manufactured of pitch-based isotropic carbon fiber bundle of 1640tex 诰

Pitch-based isotropic carbon fiber bundles (Co. Kureha, sagging force tow T_ 101 S, 23g / m) using, in Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2 , it extends in the 0-fold 4. Place this carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 4. extend in the 0-fold and one carbon fiber bundle, and further stretched to a 3 0 times 4. the carbon fiber bundle 2 together with kneading Article machine and one carbon fiber bundle, further fourth the carbon fiber bundle in kneading Article machine two together and stretched 5 times 3. give a pitch-based isotropic carbon fiber bundle of one unit 1. 64g / m (1640tex).

[0076] (Production Example 5) a heat treatment temperature 1000 ° C, the production of pitch-based isotropic carbon fiber bundle of 4000tex

Pitch-based isotropic carbon fiber bundle used (Co. Kureha, sagging force tow T- 101 S, 23g / m), and Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2 in, was stretched 5 times 3. Align the carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 3 . extend in the 0-fold and one carbon fiber bundle, and further stretched to a 3 0 fold 3. the carbon fiber bundle 2 together with kneading Article machine and one carbon fiber bundle, yet a 4 the carbon fiber bundle in kneading Article machine was stretched nine times 2.2 present combined to obtain a pitch-based isotropic carbon fiber bundle of one 4. 0 g / m (4000tex).

[0077] (Production Example 6) Preparation of PAN-based carbon fiber bundle of 660tex

200tex of PAN-based continuous filaments (manufactured by Toho Tenax Co., Besufuaito HT A- 3K) carbon fibers cut into a fiber length of 200mm using a cutting machine, aligned pull the fibers by carding machine, 10 g / obtain a fiber bundle of m. Then, in Nerijo process using a kneading Article machines three aircraft configured as shown in FIG. 2, the fiber bundles of the one in the first kneading Article machine 5. stretched 0 times as one fiber bundle further the fiber bundle 2 the combined 3. stretched nine times as one fiber bundle, further 1x 3. the fiber bundle 2 together with the third kneading Article machine in the second kneading Article machine by stretching to obtain a PAN-based carbon fiber bundle 0 of one. 66g / m (660tex) to.

[0078] (Production Example 7) heat treatment temperature 1000 ° C, manufactured of pitch-based isotropic carbon fiber bundle of 1187tex 诰

Pitch-based isotropic carbon fiber bundles (Co. Kureha, sagging force tow T_ 101 S, 23g / m) using, in Nerijo process using a kneading Article machines four aircraft configured as shown in FIG. 2 , extend in the 0-fold 5. Place this carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 5. extend in the 0-fold and one carbon fiber bundle, and further stretched to a 3 0 times 4. the carbon fiber bundle 2 together with kneading Article machine and one carbon fiber bundle, further fourth the carbon fiber bundle in kneading Article machine 2 together 3. stretched to 1x of one 1. obtain a pitch-based isotropic carbon fiber bundle of 1 87g / m (1187tex).

[0079] (Production Example 8) a heat treatment temperature 1000 ° C, the production of pitch-based isotropic carbon fiber bundle of 132tex

Pitch-based isotropic carbon fiber bundle used (Co. Kureha, sagging force tow T- 101 S, 23g / m), and Nerijo process using a kneading Article machine 5 aircraft configured as shown in FIG. 2 in, extend in the 0-fold 4. Place this carbon fiber bundle 2 in a first mixing Article machine and one carbon fiber bundle, combined further two of the carbon fiber bundle in the second kneading Article machine 5 . was stretched to twice the one carbon fiber bundle, further to extend the one carbon fiber bundle of doubling 5. the carbon fiber bundle 2 together with the third kneading Article machine, further the 4. the carbon fiber bundle in kneading Article machine combined two 5. stretched to twice the one carbon fiber bundle, further fifth kneaded Article machine at stretching the carbon fiber bundle one 5. 0 times to obtain a pitch-based isotropic carbon fiber bundle of one 0. 13 2g / m (132te X ).

[0080] (Example 1)

Obtained in Production Example 1 was heat-treating temperature 1000 ° C, the carbon fiber constituting the outer peripheral portion of the pitch-based isotropic short fiber length of carbon fiber bundles 660Tex, long fiber length charcoal PAN-based continuous filaments of 33tex Moto繊 維束(Toho Tenax Co., Ltd., Besufuaito, HTA-W05K) using as a carbon fiber constituting the core part, to obtain a hybrid carbon fiber spun yarn as follows. Chi words, by using a spinning machine having the structure as shown in FIG. 3, the short fiber length of carbon fiber bundles 32 during spinning with Z (left) twist 185 turns / m while stretched 20-fold, at the same time the long fiber length carbon fiber bundle 36 was charged through the middle rollers 37, to obtain a hybrid carbon fiber spun yarn of 66tex be blended with the short fiber length of carbon fiber bundles and a long fiber length carbon fiber bundle.

[0081] In the hybrid carbon fiber spun yarn thus obtained, the and one yarn consisting of staple fiber length-carbon fiber bundle is twisted together with the core portion consisting of the long fiber length of carbon fiber bundles , the outer circumferential surface of the core portion is completely covered by the yarns (outer peripheral portion) of convolutions around its. The hybrid carbon fiber spun yarn thus obtained was as sufficiently high uniformity of small tools fineness variation in fineness.

[0082] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0083] (Example 2)

Using pitch-based isotropic carbon fiber bundle of 920T ex obtained instead of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1 in Production Example 2, further 20tex the PAN as long fiber length carbon fiber bundle system long fiber length carbon fiber bundles of continuous filaments (long fiber length carbon fiber bundle of PAN-based continuous filaments of 33Tex (Toho Tenax Co., Ltd., Besufuaito, obtained by dividing the HTA-W1K)) and except for using in the same manner as in example 1 to obtain a hybrid carbon textiles spun yarn 66Tex. Thus structure of the hybrid carbon fiber spun yarn thus obtained are similar to those obtained in Example 1, also the uniformity of the fineness been made sufficiently high.

[0084] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0085] (Example 3)

Using pitch-based isotropic carbon fiber bundle of 398T ex obtained in Production Example 3 in place of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1, further 33tex the PAN as long fiber length carbon fiber bundle system continuous long fibers of the long fiber length of carbon fiber bundles (Toho Tenax Co., Ltd., Besufuaito, H TA_W1K) 1 present a long fiber length carbon fiber bundle of PAN-based continuous filaments obtained 13tex by dividing this except that used was a 46tex together one and in the same manner as in example 1 to obtain a hybrid carbon fiber spun yarn 66Tex. Thus construction of high Buritsudo carbon fiber spun yarn thus obtained are similar to those obtained in Example 1, also, the fineness of uniformity was sufficiently high.

[0086] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0087] (Example 4)

Long fiber length carbon fiber bundle of PAN-based continuous long fibers 33tex as long fiber length carbon fiber bundle, except for using (Toray Co., Torre force to those obtained by dividing the M40) Example 1 It was obtained in the same manner hybrid carbon fiber spun yarn 66Tex. Thus structure Ha Iburitsudo carbon fiber spun yarn thus obtained are similar to those obtained in Example 1, also the uniformity of the fineness was sufficiently high.

[0088] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0089] (Example 5)

The weave except that instead of twill plain-woven in the same manner as in Example 1, FAW there is 95g thickness to obtain a hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0090] (Example 6)

67tex 1640 pitch-based isotropic carbon fiber bundle of tex obtained in Production Example 4 instead of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1 as Yore ,, a longer fiber length of carbon fiber bundles PAN-based long fiber length carbon fiber bundles of continuous filaments (manufactured by Toho Tenax Co., Besufuaito, HTA- W1K) except for using in the same manner as in example 1 to obtain a hybrid carbon fiber spun yarn 149tex . Thus structure of the hybrid carbon fiber spun yarn thus obtained is similar to that obtained in real Example 1, also, the fineness of the homogeneity is sufficiently Kore, Monodea ivy.

[0091] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 1 50 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 20 mm.

[0092] (Example 7)

200tex 4000 pitch-based isotropic carbon fiber bundle of tex obtained in Production Example 5 instead of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1 as Yore ,, a longer fiber length of carbon fiber bundles the resulting long fiber length carbon fiber bundle of PAN-based continuous filaments (Toho Tenax Co., Ltd., Besufuaito, HTA- 3K) except for using in the same manner as in example 1, the hybrid carbon textiles spun yarn 400tex It was. Thus structure of the hybrid carbon fiber spun yarn thus obtained are similar to those obtained in Example 1, also the uniformity of the fineness been made sufficiently high.

[0093] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 5 15 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 83 mm.

[0094] (Example 8)

Long fiber length carbon fiber bundle of pitch-based anisotropic continuous long fibers 33tex as long fiber length carbon fiber bundles (Mitsubishi Chemical Functional Products Capital Corp., DIALEAD, obtained by dividing the K32112) was used otherwise in the same manner as in example 1 to obtain a hybrid carbon fiber spun yarn 66Tex. Thus structure of the hybrid carbon fiber spun yarn thus obtained are similar to those obtained in Example 1, also the uniformity of the fineness was sufficiently high.

[0095] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0096] (Example 9)

Except for using PAN-based carbon fiber bundle of 660T ex obtained in Production Example 6 in place of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1 in the same manner as in Example 1, Haiburitsu de of 66tex to obtain a carbon fiber spun yarn. Thus the configuration of the hybrid carbon fiber spun yarn obtained in a similar to that obtained in Example 1, also the uniformity of the fineness was also of enough high.

[0097] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0098] (Comparative Example 1)

Using only pitch-based isotropic carbon fiber 維束 obtained in Production Example 1 Nag that using a long fiber length carbon fiber bundles, 10 times instead of stretching the short fiber length of carbon fiber bundles 32 to 20 times except that so as to extend in the in the same manner as in example 1 to obtain a pitch-based isotropic carbon textiles spun yarn 66Tex. Thus pitch-based isotropic carbon fiber spun yarn thus obtained is variation in fineness was large Les those.

[0099] Next, obtained by plain weaving using a pitch-based isotropic carbon fiber spun yarn of the, FAW force S95g / m 2, a pitch-based isotropic carbon fiber spun yarn fabric having a thickness of 0. 12 mm It was.

[0100] (Comparative Example 2)

Long fiber length carbon fiber bundle of PAN-based continuous filaments of 67Tex (Toho Tenax Co., Beth Fight, HTA-W1K) long fiber length of carbon atoms of the PAN-based continuous filaments of 66tex obtained by dividing the by plain weave using only fiber bundle, FAW is 95gZm 2, the thickness was obtained PAN-based carbon fiber fabric of 0. 12 mm.

[0101] (Comparative Example 3)

6 1187 pitch-based isotropic carbon fiber bundle of tex obtained in Production Example 7 in place of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1 as Yore ,, a longer fiber length of carbon fiber bundles . long fiber length carbon fiber bundle of PAN-based continuous filaments of 6Tex (PAN-based continuous long fibers 33tex long fiber 維長 carbon fiber bundle (Toho Tenax Co., Ltd., Besufuaito, by dividing the HTA-W05K) except that resulting ones) it was prepared in the same manner as in example 1 to obtain a hybrid carbon fiber spun yarn 66Tex.

[0102] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0103] (Comparative Example 4)

Using pitch-based isotropic carbon fiber bundle of 132t ex obtained in Production Example 8 in place of the pitch-based isotropic carbon fiber bundle obtained in Production Example 1, further 33tex the PAN as long fiber length carbon fiber bundle system continuous long fibers of the long fiber length of carbon fiber bundles (Toho Tenax Co., Ltd., Besufuaito, H TA-W05K) length of the PAN-based continuous length textiles obtained 26. 4Tex by one and dividing this except for using what was 59. 4Tex together with the fiber length of carbon fiber bundles one in the same manner as in example 1 to obtain a hybrid carbon fiber spun yarn 66Tex.

[0104] Next, by plain weaving using a hybrid carbon fiber spun yarn of the, FAW is 9 5 g / m 2, thickness was obtained hybrid carbon fiber spun yarn fabric 0. 12 mm.

[0105] ingredients evaluation results>

Example: to 9 and Comparative Examples: density of each carbon fiber in the hybrid carbon fiber spun yarn obtained in 1-4, constituting the core portion and the outer peripheral portion, the length and tensile strength as shown in Table 1 Met. Further, the content of the long fiber length of carbon fibers and the short fiber length of carbon fibers in each hybrid carbon fiber spun yarn, and fineness of the hybrid carbon fiber spun yarn, the adhesion between the tensile strength and matrix materials in Table 1 It was as shown. Furthermore, the actual 施例:! ~ 9 and Comparative Examples: The thickness of the hybrid carbon fiber spun yarn fabric obtained in ~ 4, FA W (Fiber Area Weight) and weave were as shown in Table 1.

[table 1]

* 1: a continuous length fibers refers to more good 5m fibers (Embodiment Iramento) c

* 2: Contact t in Comparative Example 1, Te is the pitch-based isotropic carbon fiber spun yarn, your t in Comparative Example 2, Te is the length the fiber length of carbon fiber bundle of PAN-based continuous filaments.

* 3: Contact in Comparative Example 1, Te is also woven pitch-based isotropic carbon fiber spun yarn force becomes also long fibers long carbon fiber bundle strength of PAN-based speed connection long fibers Te Contact L, in Comparative Example 2 a textile.

[0107] Table 1 As is clear from the results described, the hybrid carbon fiber spun yarn of the present invention (Examples:! ~ 9), the adhesion is sufficiently between tensile strength is sufficiently high and the matrix material superior and teeth force was also confirmed that the uniformity of the mentioned above fineness is sufficiently high. Accordingly, High Priestess head carbon fiber spun yarn fabric (Example!: ~ 9) of the present invention obtained using the hybrid carbon fiber spun yarn of the present invention is excellent in adhesion and mechanical strength of the matrix material, the teeth It was excellent in uniformity of the force thickness.

Industrial Applicability

[0108] As described above, according to the present invention, hive achieve high tensile strength without lowering the adhesion with the matrix material such as a polymeric material, the tooth forces is also excellent in the uniformity of fineness Ritsudo it is possible to provide a carbon fiber spun yarn. Thus, Bruno of the present invention, Iburitsudo-carbon fiber spun yarn, the polymer fibers or the gas diffuser of the electrolyte fuel cell is very useful as a composite material reinforcing fibers such as for space aviation.

[0109] Further, according to the present invention, excellent adhesion and mechanical strength of the matrix material, the tooth forces is also possible to provide a carbon fiber spun yarn fabric also excellent uniformity of thickness. Accordingly, the hybrid carbon fiber spun yarn fabric of the present invention, the solid polymer electrolyte fuel gas diffuser of the battery, C / C composite material, a heater, textiles, as-carbon fiber woven fabric used for molding insulation material reinforcements etc. it is very useful.

Claims

The scope of the claims
[1] a core section composed mainly of carbon fibers, a hybrid carbon fiber spun yarn and a Cormorant outer peripheral portion covering the outer peripheral surface of and the core portion composed mainly of carbon fibers, forming the core portion more than 20 wt% of the fibers are longer than the fiber length of carbon fibers having a fiber length of 500 mm, more than 80% by weight of the fibers constituting the outer peripheral portion is a short fiber length of carbon fibers is less than the fiber length of 500 mm, and the length wherein the fiber length of carbon fiber mass ratio of the short fiber length of carbon fibers (long fiber length carbon fibers: short fiber length of carbon fibers) 20: 80-80: hybrid carbon fiber spun yarn 20.
[2] The long fiber length carbon fibers, pitch-based anisotropic carbon fibers, Ru least one carbon fiber der selected from the group consisting of polyacrylonitrile-based carbon textiles and rayon-based carbon fibers, in claim 1 hybrid carbon fiber spun yarn according.
[3] the short fiber length of carbon fibers are pitch-based isotropic carbon fibers and / or polyacrylonitrile-based carbon fibers, hybrid carbon fiber spun yarn of claim 1.
[4] The long fiber length carbon fibers are polyacrylonitrile-based carbon fibers, and the short fiber length of carbon fibers are pitch-based isotropic carbon fibers, hybrid carbon textiles spun yarn of claim 1.
[5] the proportion of carbon fiber and less than 500mm in fiber length 150mm or more in the short fiber length of carbon fibers are 3 to 30 wt%, the hybrid carbon fiber spun yarn according to claim 1
[6] the and the outer peripheral portion is constituted by yarn mainly containing short fiber length of carbon fiber, of the core portion by being twisted together with the core portion in which the yarn is mainly composed of long fiber length carbon fibers the outer peripheral surface is covered with the twisted yarn, the hybrid carbon fiber spun yarn of claim 1 wherein.
[7] The hybrid twist number in the carbon fiber spun yarn is 50 to 400 times Zm, hybrid carbon fiber spun yarn according to claim 6.
. [8] Density of the long fiber length of carbon fibers 1.7 to 2 was 3 g / cm 3, and the density of the short fiber length-carbon fiber 1. 5: is 1. 8 g / cm 3 hybrid carbon fiber according to claim 1
[9] is a mass (tex) force 0~150g per 1000 m, the hybrid carbon fiber spun yarn of claim 1.
Hybrid carbon fiber spun yarn fabric containing a hybrid carbon fiber spun yarn according least 30 mass% in any one of claims 1 to 9.
PCT/JP2006/302822 2005-02-22 2006-02-17 Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using same WO2006090643A1 (en)

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JP2007504688A JP4822552B2 (en) 2005-02-22 2006-02-17 Yarn hybrid carbon fiber spun and hybrid carbon fiber spun yarn fabric using the same
KR20077021949A KR101156316B1 (en) 2005-02-22 2006-02-17 Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using same
EP20060713963 EP1854911A1 (en) 2005-02-22 2006-02-17 Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using same
US11884872 US8171711B2 (en) 2005-02-22 2006-02-17 Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using the same

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JP2013100226A (en) * 2013-01-10 2013-05-23 Toyo Tanso Kk Expansible graphite sheet, protection method for carbonaceous crucible using the same, and single crystal pulling apparatus
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US20080152906A1 (en) 2008-06-26 application
KR101156316B1 (en) 2012-06-13 grant
US8171711B2 (en) 2012-05-08 grant
EP1854911A1 (en) 2007-11-14 application
CN101124355A (en) 2008-02-13 application
JP4822552B2 (en) 2011-11-24 grant
KR20070116012A (en) 2007-12-06 application
JPWO2006090643A1 (en) 2008-07-24 application
CN101124355B (en) 2010-07-28 grant

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